TWI635141B - Reactive dyes, their preparation and their use - Google Patents

Abstract

The invention relates to a reactive dye of the formula: Where Me is chromium, cobalt or iron, R ₁ is hydrogen or unsubstituted or substituted C ₁ -C ₄ alkyl, and E is a divalent radical of the formula: Where X represents chlorine or fluorine, and T is a fiber-reactive group of the formula: -NH- (CH ₂ ) _2-3 -SO ₂ -Z (2a), -NH- (CH ₂ ) _2-3 -O- (CH ₂ ) _2-3 -SO ₂ -Z (2b), (R ₃ ) _0-2 represents 0 to 2 identical or different substituents from the following groups: halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfonic group, Z is ethylene Or -CH ₂ -CH ₂ -U group and U is a group that can be removed under basic conditions, and Q is -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ group , Q is the number 0 or 1, and G is the divalent base of the following formula: Where (R ₂ ) _s represents s same or different substituents from the following groups: halogen, nitro, unsubstituted or halogen-substituted C ₁ -C ₄ alkyl, C ₂ -C ₄ alkyl Amine, C ₁ -C ₄ alkylsulfonyl, carbamoyl, sulfamoyl, sulfonic and -ET, where E and T are as defined above, and s is the number 0, 1, 2 Or 3, A represents the divalent base of the formula: Wherein R ₁ , R ₂ , X, T, q and s are as defined above, R ₄ and R ₇ represent hydrogen, C ₁ -C ₄ alkyl, -COOH or -COO-C ₁ -C ₄ alkyl, R ₅ and R ₆ each independently represent the same or different substituents from the following groups: hydroxyl, halogen, nitro, unsubstituted or halogen-substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkylfluorenylamino, C ₁ -C ₄ alkylsulfonyl, carbamoyl, sulfamoyl, and sulfonic groups, and t and u are each independently The number 0, 1, 2 or 3 is particularly suitable for dyeing synthetic polyamide fiber materials and producing dyed or printed matter with good wet fastness properties.

Description

Reactive dye, its preparation and use

The invention relates to a novel navy blue reactive dye, a preparation method thereof, and an application of dyeing or printing on textile fiber materials.

The recent practice of using reactive dyes for dyeing has made higher demands on the quality of dyed products and the economic efficiency of the dyeing process. Therefore, there is a continuing need for novel reactive dyes with improved properties, especially in terms of dye application.

Today's dyeing requires reactive dyes that are sufficiently direct and at the same time easily unwashable. It should also have good color yield and high reactivity. The goal is especially to provide dyes with a high degree of fixation. Known dyes do not meet all of their requirements for all properties.

So far, dark dyeings of polyamines have been obtained using only acid dyes, but these dyes have no wet fastness at high temperatures. Dark dyes with permanent wet fastness can only be obtained by using reactive dyes.

Therefore, a potential problem of the present invention is the discovery of novel reactive dyes for dyeing and printing improvement of fiber materials, especially when these dyes are used to dye synthetic polyamide fiber materials with the above characteristics to a high level Quality. Novel dyes should stand out with high fixation rates and high fiber-dye binding stability. Dyes should especially produce dyes with good all-round fastness properties such as light fastness, wet fastness and chlorine fastness.

In particular, there is a need for very reactive dyes that are suitable for synthetic polyamides. Microfibers are dyed and provide dyes with high light fastness and wet fastness, especially navy blue shades.

The problems raised have been found to be solved primarily by the novel dyes defined below.

The invention therefore relates to a reactive dye of the formula: Where Me is chromium, cobalt or iron, R ₁ is hydrogen or unsubstituted or substituted C ₁ -C ₄ alkyl, and E is a divalent radical of the formula: Where X represents chlorine or fluorine, and T is a fiber-reactive group of the formula: -NH- (CH ₂ ) _2-3 -SO ₂ -Z (2a), -NH- (CH ₂ ) _2-3 -O- (CH ₂ ) _2-3 -SO ₂ -Z (2b), (R ₃ ) _0-2 represents 0 to 2 identical or different substituents from the following groups: halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfonic group, Z is ethylene Or -CH ₂ -CH ₂ -U group, and U is a group that can be removed under basic conditions, and Q is -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ group Group, q is the number 0 or 1, and G is the divalent radical of the formula: Where (R ₂ ) _s represents s same or different substituents from the following groups: halogen, nitro, unsubstituted or halogen-substituted C ₁ -C ₄ alkyl, C ₂ -C ₄ alkyl Amine, C ₁ -C ₄ alkylsulfonyl, carbamoyl, sulfamoyl, sulfonic and -ET, where E and T are as defined above, and s is the number 0, 1, 2 Or 3, A represents the divalent base of the formula: Wherein R ₁ , R ₂ , X, T, m, n, q and s are as defined above, and R ₄ and R ₇ represent hydrogen, C ₁ -C ₄ alkyl, -COOH or -COO-C ₁ -C ₄ alkyl, R ₅ and R ₆ each independently represent the same or different substituents from the following groups: hydroxyl, halogen, nitro, unsubstituted or halogen-substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkylfluorenylamino, C ₁ -C ₄ alkylsulfonyl, carbamoyl, sulfamoyl and sulfonic groups, and t and u each Independent of each other are the numbers 0, 1, 2 or 3.

In the group of formula (2c), Me is methyl and Et is ethyl. In addition to hydrogen, these groups are suitable as substituents on the nitrogen atom.

As a C ₁ -C ₄ alkyl group, R ₁ to R ₇ start to consider each independently of any other such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl Or isobutyl, preferably methyl or ethyl and especially methyl. In the case of R ₁ , the alkyl group mentioned is unsubstituted or via, for example, hydroxyl, sulfo, sulfato, cyano, carboxyl, C ₁ -C ₄ alkoxy or phenyl, preferably Hydroxyl, sulfate, C ₁ -C ₄ alkoxy or phenyl substituted. For R ₁ , the corresponding unsubstituted group is preferred.

As the C ₁ -C ₄ alkyl group, R ₂ , R ₅ and R ₆ start to consider, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, or isobutyl Is preferably methyl or ethyl and especially methyl. The alkyl groups mentioned are unsubstituted or mono- or polysubstituted by halogen, such as fluorine, chlorine or bromine, preferably fluorine or chlorine.

As the C ₁ -C ₄ alkoxy group, R ₃ starts to consider, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethyl Oxygen and especially methoxy.

As a halogen, R ₂ , R ₃ , R ₅ and R ₆ start to consider, for example, fluorine, chlorine or bromine, each of which has nothing to do with any other, preferably chlorine.

As the C ₂ -C ₄ alkylamidoamino group, R ₂ starts to consider, for example, an acetamido group or a propylamido group, and an acetamido group is preferred.

As C ₁ -C ₄ alkylsulfonyl, R ₂ , R ₅ and R ₆ start to consider, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl or n-butylsulfonyl Is preferably methylsulfonyl or ethylsulfonyl.

R ₂ , R ₅ and R ₆ representing a carbamoyl group correspond to a group of the formula -CONH ₂ .

R ₂ , R ₅ and R ₆ representing sulfamoyl groups correspond to a group of the formula -SO ₂ NH ₂ .

R _{1 is} preferably hydrogen.

(R ₂ ) _s preferably represents s the same or different substituents from the following groups: halogen, nitro, C ₂ -C ₄ alkylamino and sulfonic groups, especially nitro and sulfonic groups And more particularly nitro.

(R ₃ ) _0-2 preferably represents 0 to 2 identical or different substituents from the group: C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfonate, especially methyl , Methoxy and sulfonic groups.

Formula (2c) is particularly preferably free of the substituent R ₃ .

T is preferably a group of formula (2c), (2d), (2e) or (2f), especially a group of formula (2c) or (2d) and more particularly of formula (2c).

Hal in the fiber-reactive group of the formula (2f) is preferably chlorine or bromine, especially bromine.

As the leaving group U, for example, -Cl, -Br, -F, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OPO ₃ H ₂ , -OCO-C ₆ H ₅ , -OSO ₂ -C ₁ -C ₄ alkyl or -OSO ₂ -N (C ₁ -C ₄ alkyl) ₂ . U is preferably a group of the formula -Cl, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OCO-C ₆ H ₅ or -OPO ₃ H ₂ , especially a group of -Cl or -OSO ₃ H .

Examples of suitable groups Z are therefore vinyl, β-bromo- or β-chloro-ethyl, β-acetoxyethyl, β-benzyloxyethyl, β-phosphonoethyl Β-sulfate complex ethyl and β-thiosulfate complex ethyl. Z is preferably vinyl, β-chloroethyl or β-sulfatoethyl, and is especially vinyl.

s is preferably the number 0, 1, or 2, especially the number 0 or 1, and more particularly the number 0.

q is preferably the number 0.

Me is preferably chromium.

E is preferably the divalent base of the following formula: Especially a group of formula (1a1).

The group of formula (2c) is preferably a group of the following formula:

A preferably represents the divalent base of the following formula:

In the formula (1), the substituent -NR ₁ -ET is preferably at the 8-position of the naphthyl group, in which the oxygen atom is bonded at the 1-position.

In formula (1), the second sulfonic group substituent is preferably at the 5-position or 6-position of naphthyl, most preferably the 6-position, wherein the oxygen atom is bonded to the 1-position.

The invention further relates to a method for preparing a reactive dye of formula (1) as defined above, wherein E is a group of formula (1a), the method comprising

(i) Using a suitable chromium, cobalt or iron compound, a compound of the formula: HO-A-OH (4) and Prepare a 1: 2 metal complex dye of the following formula: And (ii) in a first condensation step, the 1: 2 metal complex dye of formula (6) obtained according to (i) is condensed with a cyanur halide of the following formula:

And (iii) in a second condensation step, obtain a primary condensation product according to (ii): Condensation with a compound of formula: TH (9), or (iv) condensing a 1: 2 metal complex dye of formula (6) obtained according to (i) with a compound of formula: R ₁ , Me, X, T, A, G, and q each have the definitions given above.

A suitable cyanur halide of formula (6) is cyanuric chloride.

Compounds of formula (10) are known or can be prepared similarly to known methods, for example by condensing a cyanogen halide of formula (6) with a compound of formula (9), where T has the definition given above And better meaning.

The 1: 1 chromium complex dye of formula (6) is known or can be obtained similarly to known compounds, for example by making a 1: 1 chromium complex of the following formula: Reacting with an azo compound of formula (5), A, G, T, R ₁ and q each have the definition and preferred meaning given above.

The reaction of the 1: 1 chromium complex of formula (11) with the azo compound of formula (5) is, for example, in an aqueous medium at a temperature of, for example, 40 ° C to 130 ° C, especially 70 ° C to 100 ° C, at, for example, 8 It is carried out at a pH value of 14 to 14, especially at a pH value of 10 to 13. The reaction is more preferably carried out in the presence of an inorganic acid neutralizing medium or a basic medium, for example, in the presence of an alkali metal carbonate, an alkali metal acetate or an alkali metal hydroxide, and the alkali metal is preferably sodium.

If A is not a symmetric group, the 1: 2 metal complex of formula (6) prepared according to (i) generally includes two coordination isomers.

Except for the metal complexes disclosed in the form of a structural formula in the context of the present invention (such as the metal complexes of formulas (1), (6), and (8)), the present invention should be regarded as also including corresponding coordination isomer.

Compounds of formulae (4), (5), (9) and (11) are known or can be obtained similarly to known methods.

For example, the 1: 1 chromium complex of formula (11) can be obtained according to the conventional chrome method, wherein the reaction with the chromium salt can be, for example, in an aqueous medium, and optionally under pressure, for example, at 90 ° C to 130 ℃. Suitable chromium salts are, for example, chromium (III) acetate, chromium (III) nitrate, chromium (III) chloride, chromium (III) salicylate, and chromium (III) sulfate.

The compounds of the formulae (4) and (5) can be obtained according to conventional diazotization and coupling reactions. Diazotization is usually carried out at a low temperature of, for example, 0 ° C to 20 ° C, by the action of nitrous acid in an aqueous solution of an inorganic acid, and the coupling is suitably performed at a basic pH value, for example, at a pH value of 8 to 12.

1: 2 cobalt or iron complex dyes of azo compounds of formulae (4) and (5) are Known or available similarly to known methods.

1: 2 chromium or 1: 2 cobalt complex dyes can be similar to the methods mentioned in GB-A-716 753, GB-A-719 274, GB-A-745 641 and GB-A-851 861, for example To obtain. A 1: 2 iron complex dye can be obtained, for example, similarly to the method mentioned in US 5 376 151.

The condensation reaction is carried out in a manner known per se, and is generally carried out in an aqueous solution at a temperature of, for example, 0 ° C to 50 ° C and a pH of, for example, 2 to 10.

According to (i), the condensation of the 1: 2 metal complex dye of formula (6) with the cyanur halide of formula (7) is preferably performed at a temperature of 0 ° C to 5 ° C and a pH of 3 to 6. According to (iii), the condensation of the primary condensation product of the formula (8) with the compound of the formula (9) is preferably performed at a temperature of 0 ° C to 30 ° C and a pH of 4 to 7. According to (iv), the condensation of the 1: 2 metal complex dye of formula (5) with the compound of formula (10) is preferably performed at a temperature of 20 ° C to 50 ° C and a pH of 4 to 6.

Formula (1) is understood to include all the various coordination isomers generated during multi-stage synthesis.

In addition, formula (1) is understood to include tautomers that can be generated by proton migration.

Optionally, the final product is subjected to a conversion reaction. The conversion reaction is, for example, the conversion of the ethylenizable reactive group T (Z or Q) to its vinyl form by treatment with a dilute sodium hydroxide solution, such as β-sulfoethylsulfonyl or β- The chloroethylsulfonyl group is converted to a vinylsulfonyl group or an α, β-dihalopropionamido group is converted to an α-halopropenylamino group. These reactions are known per se. The conversion reaction is usually carried out in a neutral to alkaline medium, at a temperature of, for example, 20 ° C to 70 ° C, and at a pH of, for example, 6 to 14.

A reactive dye of formula (1) in which E is a group of formula (1b) or (1c) can be prepared in a similar manner.

The reactive dyes of formula (1) contain sulfonic groups, each of which is in the form of a free sulfonic acid or preferably in the form of a salt thereof, such as a sodium, lithium, potassium or ammonium salt, or an organic amine salt, such as three Ethanol ammonium salt.

The reactive dye of formula (1) may contain other additives, such as sodium chloride or dextrin.

The reactive dye of formula (1) of the present invention may optionally contain other adjuvants such as a buffer, a dispersant or a dustproofing agent, for example, to improve handling or increase storage stability. These adjuvants are known to those skilled in the art.

The reactive dyes of the present invention are suitable, for example, for dyeing or printing hydroxyl- or nitrogen-containing fiber materials. Examples that may be mentioned are silk, wool, various cellulosic fiber materials and polyurethane and polyamide fibers. Cellulose fiber materials are, for example, natural cellulose fibers such as cotton, flax, and hemp, as well as cellulose and regenerated cellulose. The reactive dyes of the present invention are also suitable for dyeing or printing hydroxyl-containing fibers present in blended fabrics (such as blends of cotton with polyester fibers or polyamide fibers).

It is preferred to dye or print natural or synthetic polyamide fiber materials, especially synthetic polyamide fiber materials such as, for example, polyamide 6 (poly-ε-caprolactam), polyamide 6,6 ( Polyhexamethylene adipate), Polyamine 7, Polyamide 6,12 (Polyhexamethylene dodecanoate), Polyamine 11 or Polyamine 12, with Polyamine Copolymers of 6,6 or polyamines 6, such as polymers of hexamethylene diamine, ε-caprolactam and adipic acid and polymers of adipic acid, hexamethylene diamine and isophthalic acid or adipic acid Polymers of acids, hexanediamine and 2-methylpentanediamine or 2-ethylbutanediamine. The reactive dye of the formula (1) according to the present invention is further suitable for dyeing or printing a synthetic polyamide or wool blended fabric or yarn.

The method of the invention is also advantageously applicable for dyeing or printing microfibers of synthetic polyamide. Microfiber is understood to mean a fibrous material composed of fine threads having an individual fineness of less than 1 denier (1.1 dTex). These microfibers are known and generally prepared by melt spinning.

The textile material can be in a very wide variety of processing forms, such as in the form of fibers, yarns, woven or knitted fabrics, and in the form of felt.

The reactive dye of formula (1) can be used for dyeing according to conventional dyeing and printing methods Or printing. In addition to water and dyes, the dyeing solution or printing paste may contain other additives, such as wetting agents, defoamers, leveling agents, or agents that affect the performance of textile materials, such as softeners, additives for flame retardant finishing, or Antifouling agents, water repellents and oil repellents, as well as water softeners and natural or synthetic thickeners, such as alginates and cellulose ethers.

In the case of woven felt materials, such as offset printing or space-dyed printing The method is important.

Dyeing is preferably carried out especially according to the dip dyeing method, and in the case of felt dyeing, also Dyeing can be performed according to a continuous method.

Dyeing is preferably at a pH of 2 to 7, especially 2.5 to 5.5 and more particularly 3 to 4.5 Value. The liquid ratio can be selected within a wide range such as 1: 5 to 1:50, preferably 1: 5 to 1:30. Dyeing is preferably performed at a temperature of 80 ° C to 130 ° C, especially 85 ° C to 120 ° C.

The reactive dye of formula (1) produces a leveling product with good overall properties, for example Such as good chlorine fastness, rubbing fastness, wet fastness, wet rubbing fastness, washing fastness, water fastness, seawater fastness and sweat fastness and good light fastness. It also stands out with uniform color enhancement, good affinity, high reactivity, good fixing ability and excellent lifting ability. The dye of the present invention has good water solubility and can be easily combined with other dyes.

The dye of formula (1) of the present invention is also suitable as a colorant for use in a recording system. The Such recording systems are, for example, commercially available inkjet printers for paper or fabric printing, or writing instruments such as fountain pens or ballpoint pens, and especially inkjet printers. For their purposes, the dyes of the present invention first became a form suitable for use in a recording system. A suitable form is, for example, an aqueous ink, which contains the dye of the invention as a colorant. Inks can be prepared in a conventional manner by mixing the individual components together in a desired amount of water.

As the substrate, we began to consider the above-mentioned hydroxyl-containing or nitrogen-containing fiber materials, especially natural Or synthetic polyamide fiber material. The fiber material is preferably a textile fiber material.

Also starting to consider substrates are paper and plastic film.

As examples of paper, mention may be made of commercially available inkjet printing paper, photo paper, waxed paper, coated paper Plastic paper, such as Epson Ink-jet Paper, Epson Photo Paper, Epson Glossy Paper, Epson Glossy Film, HP Special Ink-jet Paper, Encad Photo Gloss Paper, and Ilford Photo Paper. Plastic films are, for example, transparent or cloudy / opaque. A suitable plastic film is, for example, 3M Transparency Film.

Depending on the nature of use (e.g. fabric printing or paper printing), This adjusts, for example, the viscosity or other physical properties of the ink, especially those that have an affinity effect on the substrate in question.

The dye used in the water-based ink should preferably have a low salt content, that is, the total salt The content should be less than 0.5% by weight based on the weight of the dye. Dyes with relatively high salt content due to preparation and / or subsequent addition of diluents can be desalted, for example, by membrane separation procedures such as ultrafiltration, reverse osmosis or dialysis.

The total dye content of the ink is preferably 1% to 35% by weight based on the total weight of the ink wt%, especially 1 wt% to 30 wt%, and preferably 1 wt% to 20 wt%. In this case, the preferred lower limit is 1.5 wt%, preferably 2 wt% and especially 3 wt%.

Ink may comprise based on the total weight of the ink of the general terms 2wt% to 30wt%, in particular 5 wt% and preferably an amount of 30wt% to 10wt% to 25wt% of water-miscible organic solvent, for example, C ₁ -C ₄ alcohols, e.g. Methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, or isobutanol; ammonium amines, such as dimethylformamide or dimethylacetamide; ketones or Keto alcohols, such as acetone or diacetone alcohol; ethers, such as tetrahydrofuran or diacetone Alkanes; nitrogen-containing heterocyclic compounds, such as N-methyl-2-pyrrolidone or 1,3-dimethyl-2-tetrahydroimidazolone, polyalkylene glycols, such as polyethylene glycol or polypropylene glycol; C ₂ -C ₆ butanediols and thioethylene glycols, such as ethylene glycol, propylene glycol, butanediol, triethylene glycol, thioethylene glycol, hexanediol, and diethylene glycol; other polyols, For example glycerol or 1,2,6-hexanetriol; and C ₁ -C ₄ alkyl ethers of the following polyols: for example 2-methoxy-ethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, or 2- [2- (2-ethoxyethoxy) Ethoxy] ethanol; N-methyl-2-pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol is preferred.

In addition, the ink may contain a solubilizer, such as ε-caprolactam.

Especially for the purpose of adjusting the viscosity, the ink may contain natural or synthetic sources. Thickener.

Examples of thickeners that may be mentioned include commercially available alginate thickeners, starch ethers or Locust bean powder ether, especially sodium alginate itself or with modified celluloses, such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl Base cellulose or hydroxypropyl methyl cellulose is blended, and particularly preferably blended with 20 to 25 wt% carboxymethyl cellulose. Synthetic thickeners which can also be mentioned are, for example, based on poly (meth) acrylic acid or poly (meth) acrylamide and polybutanediols, such as polyethylene glycol or polypropylene glycol, having a molecular weight of, for example, 2000 to 20,000. Or thickeners of mixed polyalkylene glycols of ethylene oxide and propylene oxide.

The amount of these thickeners contained in the ink is, for example, based on the total weight of the ink 0.01 wt% to 2 wt%, especially 0.01 wt% to 1 wt%, and preferably 0.01 wt% to 0.5 wt%.

Ink may also contain buffer substances such as borax, borate, phosphate, polyphosphorus Citrate or citrate. Examples that may be mentioned include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate, and sodium citrate. Its amount is especially 0.1% to 3% by weight, preferably 0.1% to 1% by weight based on the total weight of the ink, to establish a pH value of, for example, 4 to 9, especially 5 to 8.5.

As other additives, the ink may contain a surfactant or a humectant.

Suitable surfactants include commercially available anionic or non-ionic surfactants Agent. As the humectant in the ink of the present invention, it is initially considered that an amount of preferably 0.1 wt% to 30 wt%, especially 2 wt% to 30 wt%, such as urea or sodium lactate (preferably in the form of a 50% to 60% aqueous solution), glycerin and / Or a mixture of propylene glycol.

The ink preferably has 1 to 40 mPa. s, especially 1 to 20mPa. s and more especially 1 To 10mPa. The viscosity of s.

In addition, the ink may additionally contain customary additives, such as defoamers or especially inhibiting Preservatives for fungal and / or bacterial growth. The amount of these additives is generally 0.01 wt% to 1 wt% based on the total weight of the ink.

As preservatives, start to consider formaldehyde generators, such as paraformaldehyde and three Alkanes, especially about 30% to 40% by weight aqueous formaldehyde, imidazole compounds such as 2- (4-thiazolyl) -benzimidazole, thiazole compounds such as 1,2-benzoisothiazolin-3-one or 2-n Octyl-isothiazolin-3-one, iodide, nitrile, phenol, haloalkylthio compound or pyridine derivative, especially 1,2-benzoisothiazolin-3-one or 2-n-octyl-iso Thiazolin-3-one. Suitable preservatives are for example 1,2-isothiazolin-3-one in dipropylene glycol solution of 20wt% (Proxel ^® GXL).

The ink may also contain other additives, such as fluorinated polymers or short-chain polymers, such as polyethoxy perfluoroalcohols (Forafac ^® or Zonyl ^® products), for example, in an amount of 0.01 to 1 wt% based on the total weight of the ink. .

In the case of inkjet printing, individual droplets of ink are controlled from the nozzle Spray on the substrate. The continuous inkjet method and the drop-on-demand method are mainly used for this purpose. In the case of the continuous inkjet method, droplets are continuously generated, and the printing operation does not require the droplets to be discharged into a reservoir and recycled. On the other hand, in the case of the drop-on-demand method, droplets are generated as needed and used for printing; that is, droplets are generated only when needed for a printing operation. Droplet generation can be achieved, for example, by means of a piezoelectric inkjet head or by thermal energy (bubbling). Printing by means of a piezoelectric ink jet head and printing by a continuous inkjet method are preferred.

The invention therefore also relates to an aqueous ink comprising a dye of formula (1) according to the invention, And regarding the use of the inkjet printing method of these inks for printing a variety of substrates (especially textile fiber materials), the definitions and preferences indicated above apply to these dyes, inks and substrates.

The following examples are used to illustrate the present invention. Unless otherwise specified, The temperature is given in degrees, parts are parts by weight and percentages are relative to weight percentages. Parts by weight are related to parts by volume in the ratio of kilograms to liters.

Example 1: (a) 26.4 parts correspond to the following formula

The compound in free acid form was stirred in 100 parts of water. The slurry was cooled to 0 ° C by adding about 50 parts of ice and adjusted to pH 3 using an aqueous sodium hydroxide solution, and the temperature was maintained at 0 ° C by cooling with ice. The obtained solution was slowly fed into 18.2 parts of cyanuric chloride in 20 parts of water, about 80 parts of ice and 0.2 parts of Na ₂ HPO ₄ . In the 12H ₂ O slurry, the pH was maintained at 3 by adding an aqueous sodium hydroxide solution and the temperature was maintained at 0 ° C by adding ice. Get contains the following formula

A suspension of the compound, which is indicated here in free acid form.

(b) Correspond to 39

The compound in free acid form was slurried with 550 parts of water, 15 parts of formic acid and 6.8 parts of chromium (III) acetate, and heated in an autoclave at a temperature of 100 ° C to 105 ° C for 20 hours. The pressure is about 3 bar. After cooling to room temperature, the precipitated product was filtered off, washed with water and dried under vacuum at a temperature of 50 ° C. A 1: 1 complex is obtained in free acid form, which corresponds to the following formula

(c) Correspond to 42.2

Monoazo dyes in free acid form and having been prepared from diamine 2-aminophenol and 1-amino-8-naphthol-3,6-disulfonic acid according to customary procedures and 47 parts obtained according to (b) The chromium complex was stirred together in 600 parts of water until uniform, and heated to 70 ° C. Establish and maintain a pH of 8.0 to 8.5 by adding 2N sodium hydroxide solution. Stirring is then performed at the above temperature until neither of the two starting compounds can be detected in the resulting clear solution. Get the corresponding formula

Isomeric coordination compounds in free acid form.

(d) The clear solution was cooled to 50 ° C, the pH was adjusted to about 5 by adding an aqueous hydrochloric acid solution, and the suspension obtained according to (a) was slowly added, and the pH was maintained at 5 by adding an aqueous sodium hydroxide solution. To complete the reaction, it was stirred for another two hours. Subsequently, the solution was treated with sodium hydroxide having a pH of 10-11 at room temperature for about two hours. The obtained solution was desalted by dialysis at pH 6 to 7 and concentrated to dryness by evaporation. Obtained in free acid form and corresponds to the formula

The dye of the compound and its coordination isomer (λ _max = 586 nm), the dye produces cyan-based dyes or prints with excellent overall fastness properties on amine-containing fibers.

Examples 2 to 12: Dyes of the formula:

It can be obtained in a similar manner to that described in Example 1 (except for the dyes of formulae (102) to (112) disclosed in the form of a structural formula, the present invention is also considered to include corresponding coordination isomers).

Dyeing procedure 1: 10 parts of polyamide 6,6 fiber material (Helanca tricot) were dyed in 500 parts of aqueous liquid adjusted to pH 3 with acetic acid. The proportion of the dye in Example 1 was 2% by weight of the fiber. The dyeing time at 98 ° C is 30 to 90 minutes. Then remove the dyed fibrous material, rinse with water and remove the unfixed dye in the soda washing solution at pH 10 to 11.5 and 70 ° C to 90 ° C in 20 to 30 minutes. Rinse with water and acid in an acetic acid bath After reaching pH 4, the fibrous material is dried. Obtain a navy blue dye with excellent light fastness and wet fastness properties.

Dyeing procedure 2: 70g of blended fabric composed of 72% polyamide microfibers and 28% elastic fibers. In a dyeing equipment, use 1.5 liters of a liquid containing 3g of formic acid, 0.4g of wetting agent and 0.7g of leveling agent at 40 ° C Process for 10 minutes. The pH of the liquid is 2.9. Next, 3.8 g of the dye of Example 1 previously dissolved with a small amount of water was added. The material to be dyed is treated in a dyeing solution at 40 ° C for 5 minutes, and then heated to 100 ° C and dyed at this temperature for 20 minutes. 14 g of calcium chloride were subsequently added and then stained for 40 minutes. After dyeing, the material was treated with a 1.5 liter post-treatment bath containing 2 g of 1,6-hexanediamine at 70 ° C to 90 ° C for 20 minutes. The material is then rinsed and finished in a conventional manner. Obtain deep color stains with excellent fastness properties (wash fastness according to AATCC 16E: Note 5).

To further improve the fastness properties, a conventional post-fixation step or an alkaline post-treatment can be added. For alkaline post-treatment, the dyed article was treated at 60 ° C. to 80 ° C. for 20 minutes in a fresh bath containing 2 g / l of soda and having a pH of 9.2.

Dyeing procedure 3: Use a dyeing bath containing 3 parts of the dye of Example 1 and 1 part of a commercially available thickener, 1 part of a non-ionic wetting agent, and a necessary amount of citric acid to make the dyeing bath reach pH 5.0 per 1000 parts of the dyeing bath. Continuous dyeing of polyamide 6,6 woven felt material. The woven felt material was then fixed in steam at 100 ° C. for 5 minutes, and washed and dried in a conventional manner. Woven felt material stands out with uniform navy blue dyeing with good fastness properties.

Dyeing procedure 4: Stir in a dyeing bath containing 1.6 parts of the dye of Example 1, 0.5 parts of sodium sulfate and 2 parts of sodium acetate per 100 parts of water and adjusted to pH 4.5 with acetic acid (80%) at 30 ° C. Wool knitted yarn. The liquid was boiled over a period of 45 minutes and maintained at the boiling temperature for 45 to 70 minutes. Then remove the dyed material, rinse with cold water and dry. obtain Dark blue dye with excellent fastness properties.

Printing program I

(a) Mercerized cotton satin is pad-dyed with a liquid containing 30 g / l of sodium carbonate and 50 g / l of urea (70% rolling solution ratio) and dried.

(b) Use a drop-on-demand inkjet head (bubble) to print the satin pretreated according to step (a) with an aqueous ink containing the following materials:-15wt% of the reactive dye of formula (101) in Example 1 , -15 wt% 1,2-propanediol and -70 wt% water.

The print was completely dry and fixed in saturated steam at 102 ° C for 8 minutes, cold rinsed, washed away under boiling, rinsed again and dried.

Claims (12)

A reactive dye of formula (1)

Where Me is chromium, cobalt or iron, R ₁ is hydrogen or unsubstituted or substituted C ₁ -C ₄ alkyl, and E is a divalent group of the following formula:

Where X represents chlorine or fluorine, and T is a fiber-reactive group of the following formula: -NH- (CH ₂ ) _2-3 -SO ₂ -Z (2a), -NH- (CH ₂ ) _2-3 -O- (CH ₂ ) _2-3 -SO ₂ -Z (2b),

(R ₃ ) _0-2 represents 0 to 2 identical or different substituents from the following groups: halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfonic acid group, Z is ethylene Group or -CH ₂ -CH ₂ -U group, and U is a group that can be removed under alkaline conditions, Q is -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ group Group, q is the number 0 or 1, G is the divalent group of the following formula:

Where (R ₂ ) _s represents s identical or different substituents from the following groups: halogen, nitro, unsubstituted or substituted C ₁ -C ₄ alkyl, C ₂ -C ₄ alkane Amine group, C ₁ -C ₄ alkyl sulfonyl group, carbamoyl group, sulfamoyl group, sulfonate group and -ET, where E and T are as defined above, s is the number 0, 1, Or 3, A represents the divalent base of the following formula:

And in formula (1), the substituent -NR ₁ -ET is at the 8-position of the naphthyl group, wherein the oxygen atom is bonded at the 1-position. For example, the reactive dye of formula (1) in item 1 of the patent application scope, wherein R ₁ is hydrogen. For example, the reactive dye of formula (1) in item 1 or item 2 of the patent application, wherein Z is vinyl, β-chloroethyl or β-sulfate complex ethyl. If the reactive dye of formula (1) in item 1 or item 2 of the patent application scope, where T is a fiber reactive group of the following formula:

For example, the reactive dye of formula (1) in item 1 or item 2 of the patent application, where q is the number 0. For example, the reactive dye of formula (1) in item 1 or item 2 of patent application, where s is the number 0 For example, the reactive dye of formula (1) in item 1 or item 2 of the patent application, where G represents the divalent group of formula (1d), where s is the number 0. A method for preparing a reactive dye such as formula (1) in item 1 of the patent application, where E is a group of formula (1a), which includes (i) using a suitable chromium, cobalt or iron compound, by The compound of the formula: HO-A-OH (4) and

, Preparation of 1: 2 metal complex dyes of the following formula:

And (ii) In the first condensation step, the 1: 2 metal complex dye of formula (6) obtained according to (i) is condensed with cyanuric halide of the following formula:

And (iii) in the second condensation step, the primary condensation product of the following formula is obtained according to (ii):

Condensation with a compound of the following formula: TH (9), or (iv) condensation of the 1: 2 metal complex dye of the formula (6) obtained according to (i) with the compound of the following formula:

R ₁ , Me, X, T, A, G, and q each have the definition as given in item 1 of the patent application scope. The use of a reactive dye of formula (1) as in any one of patent application items 1 to 7 or a reactive dye of formula (1) prepared by the method of patent application item 8, Used for dyeing or printing hydroxyl-containing or nitrogen-containing fiber materials. For the purpose of claim 9 of the patent application, in which natural or synthetic polyamide fiber materials are dyed or printed. An aqueous ink containing the reactive dye of formula (1) as claimed in item 1 of the patent scope. A method for printing textile fiber material, paper or plastic film according to an inkjet printing method, which includes using an aqueous ink as claimed in item 11 of the patent scope.